Poly(arylacetylenes) and thermoset resins therefrom

ABSTRACT

The invention relates to arylacetylene polymers and thermoset resins prepared therefrom. The preferred thermoset resins are prepared by copolymerizing a polyacetylenically unsaturated prepolymer with about 2 to 70% of a monomeric acetylenically unsaturated aromatic compound that has a melting point below about 185 DEG  C. and a boiling point above about 250 DEG  C. The polyacetylenically unsaturated prepolymer is a polymer of at least one polyacetylenically substituted aromatic compound such as a diethynylbenzene, which prepolymer has a number average molecular weight of about 900 to 12,000 and contains about 5 to 20% by weight of acetylenic groups. Typical monomeric acetylenic aromatic compounds that are copolymerized with the prepolymer are diphenylacetylene and diphenylbutadiyne.

This application is a continuation-in-part of copending application Ser.No. 165,592, filed July 23, 1971 now abandoned.

This invention relates to new acetylene polymers and thermoset resinsand more particularly to such polymers and resins derived fromacetylenically substituted aromatic compounds. The thermoset resins haveexceptional thermal stability, and the invention also relates to thepreparation of these resins.

High temperature resins presently available have various drawbacks whichlimit their use in many applications. A serious one frequentlyencountered is the evolution of volatiles during the curing cycle, whichmakes it imperative that the entire curing cycle be carried out underpressure. For example, polyimides when cured release volatile componentswhich cause gas bubble or void formation in the cured resin unlessconsiderable pressure is maintained during the curing operation in orderto prevent these undesirable results. When phenolic resins are cured,water is released which also causes void formation unless the curingreaction is carried out under pressure. Another disadvantage of thepreviously known high temperature resistant resins is their inability tobe molded into desired shapes by conventional methods due to their poorflow characteristics.

Now, in accordance with this invention, thermoset resins have beendiscovered which have excellent thermal properties and which can bemolded or otherwise shaped without gas evolution, hence, after forminginto the desired shape, they can be cured simply by heating, and thisoperation need not be carried out under pressure. The preferredthermoset resins of this invention comprise a copolymer of (1) aprepolymer of at least one polyacetylenically substituted aromaticcompound, said prepolymer having a number average molecular weight offrom about 900 to about 12,000 with (2) at least one acetylenicallysubstituted aromatic monomeric compound having a melting point belowabout 185° C. and a boiling point above about 250° C., said copolymerbeing essentially free of aliphatic unsaturation and predominantlyaromatic in structure. However, satisfactory thermoset resins also maybe prepared directly from the aforementioned prepolymer using certaintechniques, such as compression molding, especially with a small amountof volatile solvent present. These thermoset resins are furthercharacterized by having a flexural strength of at least about 4000p.s.i. and a flexural modulus of at least about 350,000 p.s.i.,retaining at least about 60% of said flexural modulus up to atemperature of at least about 300° C. in an inert atmosphere, retainingat least about 50% of said flexural strength and modulus and at leastabout 80% of their weight when a 30 mil thick sheet is aged in air at200° C. for 1000 hours and losing less than about 10% of their weightwhen heated, in powder form, to 500° C. at a rate of 5° per minute in aninert atmosphere.

The preferred thermoset resins of this invention are prepared by a twostage process. There is prepared, in the first stage, apolyacetylenically unsaturated prepolymer from a polyacetylenicallysubstituted aromatic compound. In the second stage, the prepolymer incombination with at least one acetylenically substituted aromaticcompound having a melting point below about 185° C. and a boiling pointgreater than about 250° C. is shaped and heated whereby resinificationtakes place. By this means it is possible to produce the thermoset resinin any desired shape since the blend of the prepolymer and theacetylenically substituted aromatic compound is readily formed into anydesired shape and this molded, or otherwise formed, article can then becured by heating and will retain its shape. When the thermoset resinsare prepared directly from the polyacetylenically unsaturatedprepolymers, a second stage reaction also, of course, is involved,namely, that of heating the prepolymer to effect curing.

PREPARATION OF THE PREPOLYMER

As already stated, the first stage in the preparation of the preferredthermoset resins of this invention is the formation of a prepolymer fromat least one polyacetylenically substituted aromatic compound, whichprepolymer is subsequently reacted in a second stage with anacetylenically substituted aromatic compound, which can be the same asthat used in the preparation of the prepolymer, or different, providedthat it has a melting point below about 185° C. and a boiling pointabove about 250° C.

The polyacetylenically substituted aromatic compound used to preparethese prepolymers can be any aromatic compound containing two or moreacetylene groups, i.e., two carbons linked by a triple bond, attached tothe same aromatic ring or to different aromatic rings in the compound,or mixtures of such compounds. The acetylenic groups can be internal,i.e., acetylene groups of the type aryl-C.tbd.C-aryl, or they can beexternal, i.e., ethynyl groups of the type aryl-C.tbd.C-H, or both typescan be present in the polyacetylenic compound. Those compoundscontaining at least one external acetylenic group are preferred sincethese are the most reactive. Generally those compounds containing onlyinternal acetylenic groups are used in admixture with a compoundcontaining at least one ethynyl group. Exemplary of thepolyacetylenically substituted aromatic compounds are m- andp-diethynylbenzenes; diethynyl toluenes; diethynyl xylenes;9,10-diethynylanthracene; diethynylbiphenyl; 9,10-diethynylphenanthrene;4,4'-diethynyl-trans-azobenzene; di(ethynylphenyl)ether;2,3,5,6-tetrachloro-1,4-diethynylbenzene; diphenyl-diacetylene (i.e.,diphenylbutadiyne); dibenzyl-diacetylene; di-p-tolyldiacetylene;di-α-naphthyldiacetylene; 1-chloro-2,5-diethynylbenzene;2,2'-dichlorodiphenyldiacetylene; 4,4'-dichlorodiphenyldiacetylene;4,4'-dibromodiphenyldiacetylene; 1,4-bis(phenylethynyl)benzene;1,3-bis(phenylethynyl)benzene; 9,10-bis(phenylethynyl)anthracene;1,3,5-triethynylbenzene; 1,2,4-triethynylbenzene;1,3,5-tris-(phenylethynyl)-2,4,6-triphenylbenzene;1,2,4-tris(phenylethynyl)-3,5,6-triphenylbenzene;tris(ethynylphenyl)benzene, etc. Monoacetylenically substituted aromaticcompounds can also be utilized in the preparation of the prepolymer as,for example, phenylacetylene, biphenylacetylene, etc.

As mentioned earlier, mixtures of the polyacetylenically substitutedaromatic compounds may be used to prepare the prepolymers. Aparticularly advantageous mixture is that of diethynylbenzene withdiphenylbutadiyne, with the latter component constituting from about 30to about 75% by weight of the total mixture. The diethynylbenzenecomponent may be m-diethynylbenzene, p-diethynylbenzene or mixturesthereof. The resulting copolymers contain about 30 to about 75% byweight of diphenylbutadiyne-derived units since the diphenylbutadiynecomponent enters the copolymer at substantially the same rate as thediethynylbenzene component. These copolymers may be cured, with orwithout addition of a monomeric acetylenically substituted aromaticcompound having a melting point below about 185° C. and a boiling pointabove about 250° C., to provide thermoset resins having the prescribedstrength and high temperature oxidation resistance properties. Inaddition, the resins derived from these copolymers have significantlyhigher elongation at break values, about 1.1 to about 1.8%, incomparison to the corresponding resins derived from diethynylbenzenehomopolymers, wherein the elongation at break values are less than 1.0%.

Another advantageous mixture is that of diethynylbenzene withphenylacetylene. Again, the diethynylbenzene component may bem-diethynylbenzene, p-diethynylbenzene or mixtures thereof. Thephenylacetylene component in this case enters the copolymer atapproximately one-half the rate of the diethynylbenzene component. Thus,considerable variation in the composition of the reaction mixture ispossible in producing copolymers containing from about 10 to about 45%by weight of phenylacetylene-derived units. The resulting copolymerswhen combined with a monomeric acetylenically substituted aromaticcompound having a melting point below about 185° C. and a boiling pointabove about 250° C., such as diphenylbutadiyne and diphenylacetylene,can be cured to provide thermoset resins having the prescribed hightemperature oxidation resistance properties. Additionally, these resinsare significantly higher in flexural strength and flexural modulus incomparison to the corresponding resins prepared from thediethynylbenzene homopolymers.

The prepolymerization reaction is carried out by heating thepolyacetylenically substituted aromatic compound with an aromatizationcatalyst. The reaction can be carried out in bulk or in the presence ofan inert diluent. Any inert diluent can be used, as, for example, etherssuch as 1,2-dimethoxyethane, dioxane and tetrahydrofuran, or aromatichydrocarbons such as benzene, toluene, xylene, etc. The amount ofdiluent used is not critical and generally will be such as to form aconcentration of the diethynylbenzene in the diluent of from 2 to 50%.Obviously, larger amounts can be used.

Any aromatization catalyst can be used to effect this cyclizationreaction. By the term aromatization catalyst is meant a catalyst thatpromotes the formation of an aromatic ring by the cyclization of threeacetylene groups. Preferred aromatization catalysts are nickel catalystssuch as nickel bis(acrylonitrile), nickel bis(acraldehyde), nickelcarbonyl bis(triphenylphosphine), nickel cyanidebis(triphenylphosphine), nickel acetylacetonate in combination withtriphenylphosphine, and the Group V-B metal halides such as niobiumpentahalides and tantalum pentahalides. The amount of the catalyst usedcan be varied widely but generally will be from about 0.5 to about 5% ofthe monomer by weight.

The polymerization is carried out by heating the polyacetylenic monomerwith the catalyst to a temperature of from about 55° C. to about 250° C.and more preferably from about 80° C. to about 150° C. Preferably thereaction is carried out in an inert atmosphere.

In carrying out the process it is essential to stop the reaction priorto complete conversion of the monomer. If the reaction is allowed to goto completion, the product is a highly cross-linked, insoluble,infusible material that cannot be plastic formed, nor can it befluidized with another acetylenically substituted aromatic compound andthen plastic formed. Hence the reaction is generally stopped at amonomer conversion above about 30% and below about 90%, and preferablyat a monomer conversion of from about 50 to about 90%. By so doing, itis possible to produce a prepolymer having a number average molecularweight of from about 900 to about 12,000, avoid the production of thevery high molecular weight polymer that is cross-linked and no longeruseful for the production of plastic formed articles and at the sametime retain in the prepolymer at least about 5%, and preferably about 5to 20%, acetylene groups by weight of the prepolymer for reaction in thesecond stage of the thermoset resin preparation. The prepolymers aresoluble in aromatic hydrocarbons and ethers.

The method by which the prepolymerization reaction is stopped and theprepolymer is isolated will, of course, depend in large measure on themethod used in preparing the prepolymer, the monomer or monomers used inits preparation, etc. If a polyacetylenically substituted aromaticmonomer of high volatility were used in the preparation of the polymer,i.e., one having a boiling point below about 250° C., then any of such amonomer remaining in the prepolymer should be removed to avoid foamingand void formation in the plastic forming and curing steps used in thepreparation of the thermoset resin in the second stage reaction. Thisremoval can be effected by vacuum evaporation or steam distillation ofthe prepolymerization reaction mixture or the reaction mixture can bemixed with a diluent which is a solvent for the monomer and anon-solvent for the prepolymer. In the latter case, the prepolymer canbe separated, as for example, by filtration, and the monomer, anyprepolymer remaining in solution, and the diluents can be recovered andrecycled in the process. Suitable diluents for precipitating theprepolymer are methanol and aliphatic hydrocarbons or mixtures thereofsuch as petroleum ether, pentane, hexane, heptane, etc.

The prepolymers of this invention are unique polymers, which in contrastto the acetylene polymers of the prior art, can be used to preparethermoset resins. It is well known that acetylene and substitutedacetylenes, as for example, phenylacetylene, can be polymerized, but thepolymers so produced are linear polymers, many of which have olefinic oracetylenic unsaturation in the polymer chain. It is also known thataliphatic compounds containing two or more acetylenic groups can bepolymerized, but again the polymer is linear and contains acetylenicunsaturation in the polymer chain. However, the instant prepolymers,prepared from a polyacetylene compound with an aromatization catalyst,differ from the prior art acetylene polymers in that they arepredominately non-linear in structure, at least 50% of the acetylenicunsaturation of the monomer having been converted during polymerizationinto aromatic structures. Furthermore, the unsaturation remaining in theprepolymer is chiefly acetylenic, which permits further polymerizationin the second stage reaction, and the prepolymer has only a low degreeof olefinic unsaturation. The acetylenic content of the prepolymer willpreferably be from about 5 to about 20% by weight of the prepolymer. Thelow degree of olefinic unsaturation is important since the presence of asignificant amount of such unsaturation leads to thermal and oxidativeinstability of the final thermoset resin at high temperature. Theformation of aromatic structures during the polymerization contributesoxidation resistant and stable linkages.

The olefinic unsaturation of the prepolymer can be determined by anuclear magnetic resonance method in which the number of hydrogen atomsattached to olefinic carbons, such hydrogens hereafter being referred toas olefinic protons, is compared with the number of hydrogen atomsattached to aromatic rings, such hydrogens hereafter being referred toas aromatic protons. The amount of acetylenic unsaturation can bedetermined by a similar technique comparing the ratio of hydrogensattached to acetylenic carbons, such hydrogens hereafter being referredto as acetylenic protons, with the aromatic protons. The prepolymer, tobe useful in the preparation of the final thermoset resin, will, asstated above, have a ratio of aromatic protons to olefinic protonsgreater than about 2.4:1 and preferably greater than about 7.5:1.

The ratio of acetylenic, aromatic and olefinic protons present in theprepolymer is determined by a nuclear magnetic resonance method usingdeuterated acetone as a solvent. The areas under the peaks near 3.63ppm., the peak at 7.48 ppm., and under the curve between 6.83 and 5.4ppm. are proportional to the number of acetylenic, aromatic and olefinicprotons, chemical shift values being measured versus an internaltetramethylsilane reference.

The amount of acetylenic protons, and so the acetylene groupconcentration, is determined quantitatively by use of an internalstandard, nitromethane added in accurate proportion to the prepolymerand giving a signal peak at 4.42 ppm.

PREPARATION OF THE MOLDING COMPOSITION

The above-described prepolymers are high melting materials and, in sofar as most thermoforming techniques are concerned, the prepolymers donot have the flow properties required for plastic forming attemperatures below the aromatization polymerization reactiontemperature. In other words, if they are heated to flow temperature thepolymerization reaction proceeds so that an infusible, insoluble andintractable product is formed. In accordance with one embodiment of thisinvention, it has been found that by adding an acetylenicallysubstituted aromatic compound that has a melting point below about 185°C. and a boiling point above about 250° C. or vapor pressure at 125° C.of less than about 20 mm., it is possible to produce a composition thatwill have sufficient flow to permit plastic formation and moreimportantly, that, when further heated after plastic forming, willcopolymerize with the acetylenic unsaturation in the prepolymer andproduce a thermoset resin.

The acetylenically substituted aromatic compounds that can be used tomodify the flow properties of the prepolymer and which are reactive(copolymerizable) with the prepolymer can be any mono- orpolyacetylenically substituted aromatic compound, which can be the sameor different from the compound used to prepare the prepolymer, providedthat this acetylenically substituted aromatic compound has a meltingpoint below about 185° C. and a boiling point above about 250° C. Forpurposes of discussion, these acetylenic compounds are referred toherein as fluidizing acetylenic compounds. Exemplary of these compoundsare betanaphthylacetylene, biphenylacetylene,4-ethynyl-trans-azobenzene, diphenylacetylene, di-m-tolylacetylene,di-o-tolylacetylene, bis(4-ethylphenyl)acetylene,bis(3,4-dimethylphenyl)acetylene, bis(4-chlorophenyl)acetylene, phenylbenzoyl acetylene, betanaphthylphenylacetylene,di(alpha-naphthyl)acetylene, 1,4-diethynylnaphthalene,9,10-diethynylanthracene, 4,4'-diethynylbiphenyl,9,10-diethynylphenanthrene, 4,4'-diethynyl-transazobenzene,4,4'-diethynyldiphenyl ether, 2,3,5,6-tetrachloro-1,4-diethynylbenzene,diphenylbutadiyne, di-p-tolyl-diacetylene, dibenzyl-diacetylene,2,2'-dichlorodiphenyl diacetylene, 3,3'-dichlorodiphenyl diacetylene,di(alpha-naphthyl)diacetylene, diethynyldiphenyl butadiyne, etc.

Just how the acetylenically substituted aromatic compound acts on theprepolymers to produce a plastic formable composition is not known. Itis believed that in part it acts as a plasticizer, making it possible toshape the infusible prepolymer, and in part that it undergoes a partialreaction with the prepolymer. In any event, such acetylenic fluidizers,unlike ordinary plasticizers, react with the prepolymer when the plasticformed composition is cured and hence become a part of the finalthermoset resin.

The amount of the acetylenic fluidizer incorporated in the prepolymercan be varied over a wide range, but generally will be from about 2 toabout 70% by weight of the prepolymer and preferably from about 5 toabout 40%. The acetylenic fluidizer can be incorporated in theprepolymer in a variety of ways. One of the simplest methods is to mixthe two in a diluent that is a solvent for the two and which ispreferably low boiling for ease in removing the diluent after the mixingoperation. Suitable diluents for this purpose are methylene chloride,dichloroethane, acetone, methyl ethyl ketone, benzene, toluene, etc.Such diluents can be removed, after adequate mixing has been achieved,by evaporation, distillation, etc. The mixing operation can be carriedout at any convenient temperature, generally at room temperature. On theother hand, if the monomer or monomers used for the preparation of theprepolymer have boiling points above about 250° C., the unreactedportion does not need to be removed from the prepolymer and can act asall or part of the fluidizer in the molding composition.

There can also be incorporated in the molding composition fillers,pigments, antioxidants and other desired additives. When the preferredcompositions containing an acetylenic plasticizer are prepared, theadditives are readily incorporated at the time the prepolymer and theacetylenic plasticizer are mixed and while the mixing diluent is stillpresent. Exemplary of the materials that can be incorporated are organicand inorganic fibrous materials such as graphite, glass, asbestos,metals, metal oxides, metal carbides, boron, boron carbide, siliconcarbide fibers, and particulate reinforcements such as glass beads,metal oxides, metal carbonates, clay, diatomaceous earth, etc. Theamount of the filler incorporated in the molding composition can bevaried widely, but generally will be from about 5 to 70 percent byweight of the composition.

After removing the mixing diluent, the plastic composition so obtainedcan be divided by any desired means into suitable size pieces for theplastic shaping operation. Alternatively, the composition can be groundto a fine powder and converted into pellets convenient for utilizationin subsequent shaping operations by compacting under pressure at roomtemperature or at a somewhat elevated temperature. These moldingcompositions are stable and can be stored at room temperature.

FORMATION OF THE THERMOSET RESIN

In the case of a prepolymer modified with an acetylenic fluidizer thecomposition will melt on heating and remain sufficiently fluid so thatit can be shaped by conventional plastic forming such as extrusion,compression, transfer and injection molding, calendering, forging, etc.Thus, shapes such as sheets, pipes, rods and wire coatings can be madeby extrusion. Sheets can in subsequent operations be further modified inform as by embossing or thermoforming. More complex shapes can be madeby molding operations. The temperature employed in the plastic formingoperation can be varied widely, the preferred temperature beingdependent on the amount of the acetylenic fluidizer employed, themolecular weight of the prepolymer, the type and amount of any filler orreinforcing agent present, the fabrication method, the pressureemployed, and the amount of cross-linking desired during the shapingoperation. Temperatures as low as about 40° C. can be used, or as highas 200° C., but generally will be within the range of from about 90° C.to about 165° C. As the heating continues above about 90° C., andgenerally at a pressure of from about 15 to about 15,000 p.s.i., themolding composition resolidifies into the desired shape. In operationssuch as extrusion or injection molding in which it may be desirable torecycle scrap material, low temperatures are employed to avoid muchchange in the flow properties of the composition during the fabrication.In other operations such as transfer or compression molding, it may bedesirable to fabricate the material at an elevated temperature so thatcross-linking or curing of the material occurs during the shapingoperation. This is one method of operation applicable to the compressionmolding of the prepolymers directly to thermoset resins. However, theprepolymers, preferably in finely-divided form, also may bepreliminarily shaped by application of pressure alone, and then heatedto effect curing.

After the shaping operation and heating above 90° C. for a sufficienttime to solidify the material, continued application of pressure duringsubsequent curing is not necessary. The further polymerization orcross-linking reaction to form the insoluble, thermally stable resindoes not involve formation of any gaseous or volatile materials andaccordingly there is no foaming or void formation. The molded or shapedarticle can then be converted to a thermoset resin by additionalheating.

The temperature at which the molding composition is heated to effect thefurther polymerization and cross-linking, which can be referred to asthe curing operation, can be varied widely and will depend on suchfactors as the components of the molding composition, the size and shapeof the fabricated article, etc. In general, the conditions for effectingthe cure will range from several hours at a temperature of about 100° C.to a few minutes at a temperature of about 300° C. Alternatively, afabricated article can be used in its only partially cured form, andcuring can be effected during use at an elevated temperature.

The reaction that takes place during the curing of the moldingcomposition containing an acetylenic fluidizer is a copolymerizationreaction between the prepolymer and the acetylenic fluidizer, whichreaction at the same time effects cross-linking of the prepolymer.Hence, the final thermoset resin can be defined as a copolymer of theprepolymer and the acetylenic fluidizer. In the case of a moldingcomposition containing no acetylenic fluidizer, the reaction duringcuring is one of further polymerization of the prepolymer.

The thermoset resins so produced are hard, stiff, strong, abrasionresistant, infusible and insoluble. They retain strength, stiffness andinsolubility at elevated temperatures, are stable to exposure atelevated temperatures for extended periods, and are resistant tooxidative attack at elevated temperature. Their oxidative stability canbe further enhanced by incorporation of inorganic stabilizers such asammonium biphosphate, calcium hypophosphite, etc. They are highlyresistant to chemical attack by strong acids and concentrated alkali. Aspreviously stated, these thermoset resins are characterized by having aflexural strength of at least about 4000 p.s.i. and a flexural modulusof at least about 350,000 p.s.i., retaining at least about 60% of saidflexural modulus in an inert atmosphere up to a temperature of at leastabout 300° C., retaining at least about 50% of said flexural strengthand modulus and at least about 80% of their weight when a 30 mil thicksheet is aged in air at 200° C. for 1000 hours and losing less thanabout 10% of their weight when heated, in powder form, to 500° C. at arate of 5° per minute in an inert atmosphere. Obviously, these valuescan be greatly increased by the addition of fillers and otherstrengthening additives.

By the terms "flexural strength" and "flexural modulus" is meant thestrength and modulus as measured according to the procedure described inASTM #D-790-70 - Flexural Properties of Plastics.

The new thermoset resins of this invention are useful as thermosettingbinder resins for glass, carbon, asbestos and boron fibers and in thepreparation of moldings to be used in high temperature environments, asfor example, turbine blades for jet engines, aeroplane wing edges,ablative coatings for space re-entry vehicles, etc.

The following examples will illustrate the preparation of theprepolymers, the molding compositions and the thermoset resins of thisinvention. All parts and percentages are by weight unless otherwiseindicated.

EXAMPLE 1 Preparation of the Prepolymer

A polymerization vessel with a nitrogen atmosphere was charged with 71parts of p-diethynylbenzene, 1.062 part of nickel acetylacetonate, 2.124parts of triphenylphosphine and 737 parts of anhydrous dioxane. Theclear pale-green solution was then heated, while stirring, to refluxtemperature and held there until the desired conversion level of 57% wasachieved. This was determined by withdrawing an aliquot periodically,cooling the aliquot to room temperature, pouring it into 5 volumes ofpetroleum ether, drying and weighing the precipitate. When the desiredconversion was reached (1 hour, 50 minutes), the reaction mixture waspoured into 5 volumes of petroleum ether. A dark, tarry massprecipitated. The supernatant was separated and filtered. The solidswere allowed to air dry and then were washed with petroleum ether anddried. The product so obtained was a brown powder. It had a numberaverage molecular weight of about 2900. Analysis by NMR as describedabove showed the prepolymer to have a ratio of aromatic protons toolefinic protons of greater than 30:1. The prepolymer contained 15.0%acetylene groups.

Preparation of Thermoset Resin

A molding composition was prepared by mixing 50 parts of a calcineddiatomaceous earth containing 93-95% SiO₂, which had previously beendried by heating to 300° C. and cooling under anhydrous conditions, 8.5parts of diphenylacetylene, and 41.5 parts of the above preparedprepolymer, adding enough acetone to dissolve the two organic materialsand to obtain better mixing with the filler. The acetone was thenevaporated in an air stream and then under vacuum. The moldingcomposition so obtained was a fine cocoa-brown powder.

The mold used for molding this composition was a semi-positive 21/4 inchdisk mold. Into the mold at room temperature was placed an aluminumdisk, 5.3 g. of the molding composition, and a second aluminum disk. Themale part of the mold was inserted and the mold was placed in apreheated hydraulic press, the temperature of the molding sample beingmonitored by means of a thermocouple. The temperature of the sample wasincreased to 275° C. during 50 minutes heating under a pressure of 1500p.s.i. The heaters were turned off (final temperature of sample 280°C.), the pressure released and the mold was cooled. After a total timeof 1 hour, 40 minutes, the mold was removed from the press and quenchedin cold water. The molded disk so obtained was hard and shiny brown. Ithad a density of 1.54, and a Barcol hardness (No. 935-1) of 75. Flexuralproperties were determined to be: strength -- 4,520 p.s.i.; modulus --860,000 p.s.i.; and elongation 0.54%.

A second molding was made from the same molding composition but thesample was heated in 16 minutes to 165° C. under 2000 p.s.i. pressure.At this point the heaters were turned off, the pressure reduced to zeroand cooling water turned on in the platens. In 8 minutes the mold wasremoved from the press and quenched in cold water. The molded disk had adensity of 1.46 and a Barcol hardness of 59. Its flexural strength was4500 p.s.i., modulus was 730,000 and elongation was 0.62%. It waspartially soluble in benzene. This sample was cured further by heatingin an air oven at atmospheric pressure at 200° C. for 3 hours. It thenhad a density of 1.58 and a hardness of 81. The flexural strength was6500 p.s.i., modulus was 1,100,000 p.s.i. and elongation was 0.59%. Itwas completely insoluble in benzene.

Another molding composition was prepared using the above preparedprepolymer, but omitting the diphenylacetylene. The prepolymer wasblended with 50% by weight based on the prepolymer of the calcineddiatomaceous earth. Acetone was added to dissolve the prepolymer and toobtain better mixing with the filler. The acetone then was evaporatedunder vacuum. The molding composition so obtained was molded in a 1-inchdiameter positive disk mold. The mold temperature was 150° C. and themold pressure was 9000 p.s.i. The molded part then was post-cured for 2hours at 250° C. and atmospheric pressure. The molded disk so obtainedhad a flexural strength of 7220 p.s.i. and a flexural modulus of1,730,000 p.s.i.

EXAMPLE 2 Preparation of Prepolymer

A prepolymer was prepared from p-diethynylbenzene as described inExample 1 except that the amount of catalyst used was reduced byone-third and the polymerization was carried out for 4 hours to aconversion of 42%. The prepolymer had a number average molecular weightof 2000, contained 15.5% acetylene groups and had a ratio of aromaticprotons to olefinic protons of greater than 30:1.

Preparation of Resin

A molding composition was prepared as described in Example 1. Disks werethen molded from a mixture of 65 parts of this molding composition and35 parts of the molding composition prepared in Example 1. In this casethe sample disks were heated to 300° C. in 47 minutes at a maximumpressure of 2300 p.s.i., after which time the heaters were turned off,the pressure reduced and the mold cooled for 40 minutes. The disk soobtained was a hard brown disk. It had a density of 1.61, flexuralstrength of 4460 p.s.i., flexural modulus of 840,000, elongation of0.55% and a Barcol hardness of 76. After aging for 4.5 hours at 320° C.in air, the flexural strength was 4750, the flexural modulus was 775,000and the elongation was 0.62%.

EXAMPLE 3

This example demonstrates the effect of the acetylenic fluidizer on theprepolymer and the molding composition prepared therefrom.

A prepolymer was prepared from p-diethynylbenzene following the generalprocedure described in Example 1 except that the prepolymerization wascarried to a monomer conversion of 30%. The prepolymer had a numberaverage molecular weight of 1050, contained 16.5% acetylene groups andthe aromatic proton to olefinic proton ratio was greater than 30:1.Molding compositions were prepared from this prepolymer as described inExample 1 but omitting the diatomaceous earth filler and using varyingamounts of the diphenylacetylene (DPA). The viscosity of these moldingcompositions at various temperatures and the changes therein with time,the temperature being changed at a heating rate of 10° per minute, istabulated below:

    ______________________________________                                        % DPA      Temp. ° C.                                                                        Viscosity (× 10.sup.5 poise)                      ______________________________________                                        0          23         Too high to measure                                                100        1200                                                               120        1000                                                               130         900                                                               150        Too high to measure                                     5          23         Too high to measure                                                90         1500                                                               120         700                                                               140        Too high to measure                                     10         23         Too high to measure                                                80          500                                                               110         100                                                               130        Too high to measure                                     20         23         Too high to measure                                                80         70                                                                 110        1.0                                                                128        Too high to measure                                     30         23         Too high to measure                                                80         2.0                                                                95          0.05                                                              128        Too high to measure                                     40         23         Too high to measure                                                60         0.6                                                                75         0.1                                                                125        Too high to measure                                     ______________________________________                                    

These data demonstrate the fluidizing action of the acetylenic fluidizerand at the same time show that reaction between the prepolymer andacetylenic fluidizer occurs at temperatures above about 90° C. Each ofthese melts could be held for several hours at temperatures up to 80° C.At temperatures above 100° C., their viscosity increased andsolidification occurred in a short time.

EXAMPLES 4 AND 5

A prepolymer was prepared from para-diethynylbenzene following thegeneral procedure described in Example 1, using 150 parts of monomer,1.8 parts of nickel acetylacetonate and 3.9 parts of triphenylphosphinein 1300 parts of benzene as diluent and reacting at reflux temperatureto 78% conversion. The prepolymer had a number average molecular weightof 5000, contained 13.0% acetylene groups and the ratio of aromaticprotons to olefinic protons was 10:1.

Molding compositions were prepared from this prepolymer using 30% of anacetylenic fluidizer and no filler. Disks were then molded from thesecompositions by heating for 6 minutes at 150° C. under 1000 p.s.i. andcured by heating for 5 hours at 250° C. at atmospheric pressure. Theflexural properties determined on them are tabulated below.

    ______________________________________                                        Acetylenic     Flexural                                                       Fluidizer      Strength (p.s.i.)                                                                           Modulus (p.s.i.)                                 ______________________________________                                        4,4'-diethynyldiphenyl                                                        ether          6008          1,148,333                                        diphenylbutadiyne                                                                            7146          1,390,670                                        ______________________________________                                    

EXAMPLE 6

A mixture of 90 parts of meta-diethynylbenzene and 10 parts ofpara-diethynylbenzene was dissolved in 840 parts of anhydrous benzenecontaining 11 parts of chlorobenzene. The solution was sparged withnitrogen and heated to reflux temperature. A suspension of 1.5 parts ofnickel acetylacetonate in 13 parts of benzene was added and then asolution of 3.0 parts triphenylphosphine in 25 parts of benzene. Thesolution was held at reflux temperature for 4.75 hours which was aconversion of 70%. The solution was then poured into 8000 parts ofpetroleum ether and the yellow powder, separated by filtration, amountedto 30 parts. The prepolymer had a number average molecular weight of4500, contained 13.9% % acetylene groups and had a ratio of aromaticprotons to olefinic protons of 10:1.

Molding compositions were prepared from this prepolymer by adding 5, 10,20 and 30% by weight of diphenylacetylene. Disks were molded from eachby heating at 150° C. for 6 minutes under 1000 p.s.i. pressure and thenwere cured by heating for 2 hours at 250° C. at atmospheric pressure andthe flexural properties were determined. The prepolymer itself, with noadded diphenylacetylene, also was molded, using 9000 p.s.i. pressure.

    ______________________________________                                                    Flexural                                                          Diphenylacetylene                                                                           Strength (p.s.i.)                                                                            Modulus (p.s.i.)                                 ______________________________________                                        0%            9500           1,140,000                                        5%            6700           1,100,000                                        10%           5700           1,200,000                                        20%           5100           850,000                                          30%           4500           600,000                                          ______________________________________                                    

EXAMPLE 7

A polymerization vessel with a nitrogen atmosphere was charged with 3.0parts of 4,4'-diethynylbiphenyl, 0.15 part of bis(triphenylphosphine)nickel dicarbonyl and 100 parts of anhydrous dioxane. The solution washeated under nitrogen on a steam bath and refluxed for 1 hour. About 65%of the monomer had been converted in this time to a prepolymer having anumber average molecular weight of 3000. The solution was thenevaporated to dryness and dried under a high vacuum.

A film was prepared from the yellow solid so obtained, which was amixture of 65% prepolymer and about 35% of unreacted monomer, by heatingthis solid on a steel plate at 160° C. This film was then cured undernitrogen at atmospheric pressure at 255°-258° C. for 4 hours. This filmhad a weight loss of only 8% on heating in air to 500° C. at a rate of5° per minute.

EXAMPLE 8

Example 7 was repeated except that di(4-ethynylphenyl) ether wassubstituted for the 4,4'-diethynylbiphenyl used in that example and theprepolymerization reaction time was 2 hours. After removal of thedioxane solvent, there was obtained a very viscous, gummy, yellow solid,which was a mixture of 60% prepolymer, with a number average molecularweight of about 2500, and 40% unreacted monomer. The material was formedinto a film at 150° C. and cured at 250° C. for 4 hours. The cured filmhad a weight loss in air of 9% when heated to 500° C. at a rate of 5°per minute.

EXAMPLES 9 AND 10

A prepolymer was prepared, following the general procedure described inExample 1, using as the monomer a mixture of 90% meta- and 10%para-diethynylbenzene, 0.26% nickel catalyst and polymerizing to aconversion of 80%. The prepolymer had a number average molecular weightof 5500, contained 12.8% acetylene groups and had an aromatic proton toolefinic proton ratio of 13:1.

Three molding compositions were prepared from this prepolymer byblending it with 10% by weight of 1,4-diphenylbutadiyne and additionallyadding 10 parts per hundred parts of the blend, of a stabilizer to twoof them.

Disks 30 to 35 mils thick and one inch in diameter were prepared andcured by heating for 5 hours at 250° C. These disks were then heated ina forced air oven at 260° C. The time, in hours, at this temperature togive a 10% weight loss of the resin is tabulated below.

    ______________________________________                                                             Time to 10% wt. loss                                     Stabilizer Added     at 260° C.                                        ______________________________________                                        None                 221                                                      Ammonium biphosphate 500                                                      Calcium hypophosphite                                                                              566                                                      ______________________________________                                    

EXAMPLE 11

Into an argon flushed reaction vessel was placed 20 parts of1-chloro-2,5-diethynylbenzene and 70 parts of benzene. The vesselcontents were stirred and heated to reflux. A solution of 0.05 part ofnickel acetylacetonate in 4.5 parts of benzene at 40° C. was addedfollowed by a solution of 0.15 part of triphenylphosphine in 4.5 partsof benzene. The solution was allowed to reflux for 1.5 hours, at whichpoint about 80% of the monomer had been converted to prepolymer. Thesolution was cooled and poured into 5 volumes of methanol. The brownsolid that precipitated was filtered, washed and vacuum dried. The yieldof polymer was 9.0 parts. The prepolymer had a number average molecularweight of 7000, contained 11% acetylene groups and the aromatic toolefinic proton ratio was 6:1. This prepolymer material was mixed with0.9 part diphenylbutadiyne and molded at 150° C. and cured atatmospheric pressure at 250° C. for 2 hours. The resulting resin had aflexural strength of 5000 p.s.i. and a flexural modulus of 600,000p.s.i.

EXAMPLE 12

A prepolymer was prepared as described in Example 1, theprepolymerization reaction being carried to a monomer conversion of 90%.This prepolymer had a number average molecular weight of 9700, contained9.5% acetylene groups and had an aromatic to olefinic proton ratio of8:1. It was blended with 10%, by weight, of diphenylacetylene in benzeneand the benzene was then removed by evaporation. The blend was molded ina picture frame mold at 140° to 150° C. for 6 minutes under 6000 p.s.i.pressure and then cured at atmospheric pressure by heating for 2 hoursat 250° C. The resin had a flexural strength of 6700 p.s.i. and aflexural modulus of 890,000 p.s.i. Repeated flexural modulusmeasurements were carried out on this molding at increasing temperature.The following data were obtained:

    ______________________________________                                        Temp., ° C.                                                                             Flexural Modulus (p.s.i.)                                    ______________________________________                                        42               860,000                                                      103              870,000                                                      145              750,000                                                      183              780,000                                                      231              720,000                                                      300              700,000                                                      326              660,000                                                      ______________________________________                                    

EXAMPLE 13 Preparation of Prepolymer

A polymerization vessel with an argon atmosphere was charged with 45parts of meta-diethynylbenzene, 5 parts of paradiethynylbenzene, 360parts of benzene and 2.2 parts of monochlorobenzene. This solution wasthen heated, while stirring, to reflux temperature and held there. Asolution of 1 part of triphenylphosphine in 18 parts of benzene wasadded under a blanket of argon and then a suspension of 0.5 part ofnickel acetylacetonate in 9 parts of benzene was added. After 6.33 hoursof refluxing, 88.5% of the mixture of diethynylbenzenes had polymerized,as determined by gas-liquid chromatographic analysis of the mixture. Thesolution was cooled and poured into 7 volumes of petroleum ether. Ayellow powder precipitated which was filtered, washed with freshpetroleum ether and vacuum dried to yield 32 parts of yellow powderypolymer. It had a number average molecular weight of about 8500. Asdetermined by NMR, it had an acetylene content of 13.4% and a ratio ofaromatic protons to olefinic protons of 15.1:1.

Preparation of Thermoset Resin

A molding composition was prepared by mixing 50 parts of calcineddiatomaceous earth containing 93-95% SiO₂, 5 parts of1,4-diphenylbutadiyne, and 45 parts of the above prepolymer, addingenough benzene to dissolve the two organic materials and to obtainbetter mixing with the filler. The benzene was then removed undervacuum. The molding composition so obtained was a fine yellowish-brownpowder.

The powder was charged to a fully positive circular mold preheated to150° C. in a hydraulic press. Then 9000 p.s.i. pressure was applied.After 6 minutes, the mold was removed from the press. Then, while stillhot, the hard, dark brown molded disk was removed, and post-cured at150° C. for 24 hours and at 250° C. for 5 hours under atmosphericpressure. The flexural properties were determined to be: strength, 8600p.s.i.; modulus, 1,450,000 p.s.i.

EXAMPLE 14

A copolymer prepolymer of diethynylbenzene and phenylacetylene wasprepared in refluxing benzene solvent. The polymerization vessel wascharged with 60 parts of a 90:10 mixture of m- and p-diethynylbenzenes,60 parts of phenylacetylene, 600 parts of benzene and 2 parts ofchlorobenzene. After heating to reflux, 5 parts of a catalyst solutionprepared by adding 0.3 part of nickel acetylacetonate and 0.6 part oftriphenylphosphine in 15 parts benzene were added. After 2 hours, anadditional 10 parts of this catalyst solution was added. After 5 hours,gas-liquid chromatographic analysis showed that 74% of thediethynylbenzenes and 35% of the phenylacetylene had been converted tocopolymer. The copolymer was precipitated by adding the solution to fivetimes its volume of petroleum ether, 26 parts being recovered. Thisproduct had a number average molecular weight of about 3,000, anacetylene content of 8.9%, and an aromatic to olefin proton ratio of5.5:1.

A molding composition was prepared from this prepolymer by adding 10% byweight of diphenylbutadiyne and disks were molded using a moldtemperature of 150° C. for 6 minutes with 2000 p.s.i. pressure, followedby curing 2 hours at 250° C. at atmospheric pressure. The flexuralproperties were found to be: strength -- 8230 p.s.i.; modulus --1,110,000 p.s.i.

EXAMPLE 15

A copolymer prepolymer of diphenylbutadiyne and p-diethynylbenzene wasprepared in refluxing benzene solvent. The polymerization vessel wascharged with 63 parts of diphenylbutadiyne, 2 parts of diethynylbenzene,600 parts of benzene, and 2 parts of chlorobenzene. After heating toreflux, 2 parts of a catalyst mixture prepared by mixing 2 parts ofnickel acetylacetonate and 4 parts of triphenylphosphine in 20 parts ofbenzene were added. After 1 hour, an additional 10 parts ofdiethynylbenzene was added. After 2 hours, 10 parts of diethynylbenzeneand 2 parts of catalyst solution were added. After 3 hours, 20 parts ofdiethynylbenzene and 4 parts of catalyst solution were added. After atotal reaction period of 7 hours, gas-liquid chromatographic analysis ofthe reaction mixture showed that 10% of each of the monomeric componentsremained. The solution was added to 5 times its volume of methanol, and77 parts of the copolymer was precipitated. It had an acetylene contentof 8.4% and an aromatic to olefin hydrogen ratio of 8:1.

A molding composition was prepared from this prepolymer by adding 5% byweight of diphenylbutadiyne and 10% by weight of calcium hypophosphite.Disks were molded using a mold temperature of 150° C. for 6 minutes at2000 p.s.i., followed by curing outside the mold 2 hours at 250° C. atatmospheric pressure. The flexural properties of these cured disks werefound to be: strength -- 5000; modulus -- 650,000 p.s.i.

EXAMPLE 16

A prepolymer was prepared, following the procedure of Example 1, usingp-diethynylbenzene as the monomer and carrying the reaction to 62%monomer conversion. The prepolymer had a number average molecular weightof 2600, an acetylene content of 15.0% and an aromatic to olefinhydrogen ratio of 38:1. This prepolymer was blended with 20% by weightof diphenylacetylene, and disks 30 mils thick and one inch in diameterwere prepared by compression molding at 150° C. for 6 minutes under 2000p.s.i. pressure, followed by curing at atmospheric pressure for 2 hoursat 250° C. The flexural strength of a sample as cured was 6040 p.s.i.and the flexural modulus was 950,000 p.s.i. Another sample disk was agedin an air oven at 230° C. for 1000 hours. At the end of this period itwas found to have lost 10.5% of its weight and on testing at roomtemperature it had a flexural strength of 3390 p.s.i. and a flexuralmodulus of 614,000 p.s.i.

One of the disks was ground to a fine powder (passing 100 mesh screen)and was tested for weight loss by thermogravometric analysis by heatingin a nitrogen atmosphere to 500° C. at a rate of 5° per minute. Theweight loss at 500° C. was 6%.

EXAMPLE 17

A prepolymer was prepared following the procedure of Example 6. Moldingcompositions were prepared from this prepolymer by adding 5, 10, 20 and30% by weight of diphenylbutadiyne (DPBD). The viscosity of thesecompositions and of the prepolymer itself at various temperatures asdetermined at a heating rate of 10° C. per minute is tabulated below:

    ______________________________________                                        % DPBD     Temp. ° C.                                                                         Viscosity (×  10.sup.5 poise)                    ______________________________________                                         0         100         50                                                                140         6                                                                 160         100                                                     5          80         20                                                                100         8                                                                 120         3.5                                                               160         Too high to measure                                    10          60         40                                                                 80         9                                                                 120         1                                                                 160         25                                                     20          60         10                                                                 80         3                                                                 120         0.3                                                               140         0.2                                                               160         4                                                      30          60         4                                                                  80         1.5                                                               100         0.05                                                              140         0.01                                                              160         0.02                                                   ______________________________________                                    

EXAMPLE 18

A prepolymer was prepared following the procedure of Example 6, exceptthat the monomer mixture was 60% meta-diethynylbenzene and 40%para-diethynylbenzene. This prepolymer was molded in a one-inch diameterpositive disk mold at a mold pressure of 9000 p.s.i. and a moldtemperature of 150° C. The molded disk was post-cured at 250° C. andatmospheric pressure for 5 hours. The cured disk had a flexural strengthof 7525 p.s.i. and a flexural modulus of 1,011,590 p.s.i.

EXAMPLE 19

Twenty-two and one-half parts of a prepolymer prepared according to theprocedure of Example 6 and two and one-half parts 1,4-diphenylbutadiynewere dissolved in benzene. Ten parts of short chrysotile asbestos fiberwas added and dispersed with magnetic stirring. The benzene was thenremoved on a rotary flash evaporator under reduced pressure. Twenty-onegrams of the resulting composite was charged to a four-inch diameter,fully positive, disk mold and compression-molded for six minutes at160°-180° C. under a pressure of 2400 p.s.i., and cured by heating for16 hours at 200° C. under atmospheric pressure. Strips three-eighths ofan inch in width were cut from the disk and found to have a flexuralstrength of 8690 p.s.i. and a flexural modulus of 1,800,000 p.s.i.

EXAMPLE 20

Eleven tows, eight inches in length, of surface-treated graphite fiber(Courtaulds) were coated with a benzene solution of 2.09 g. of aprepolymer prepared according to the procedure of Example 6 and 0.11 g.of 1,4-diphenylbutadiyne. After benzene evaporation, the tows werecollimated in a fully positive, open-ended bar mold (bar size 1/4 inch ×6 inches), compression-molded for six minutes at 143°-166° C. under apressure of 5300 p.s.i. and then cured for 18 hours at 200° C. underatmospheric pressure. The resulting bar contained 51% by volume ofgraphite fiber as determined by resin burn-off at 390° C. for 72 hours.Prior to resin burn-off, the composite was found to have an averageflexural strength of 90,950 p.s.i. and a flexural modulus of 13,900,000p.s.i.

EXAMPLE 21

Eight plies of 21/4 inches × 33/4 inches treated glass cloth were coatedwith a benzene solution of 9.0 g. of a prepolymer prepared according tothe procedure of Example 6 and 1.0 g. of 1,4-diphenylbutadiyne, and thebenzene was evaporated. The plies were then stacked, placed in a 1/16inch thick, semipositive, picture frame mold, compression-molded forfive minutes at 170° C. and a pressure of 750 p.s.i., and then cured byheating for 18 hours at 230° C. under atmospheric pressure. Theresulting laminate contained 51.7% by volume of glass as determined byresin burn-off as in Example 20. Strips were cut from the laminate andwere found to have a flexural strength of 26,600 p.s.i. and a flexuralmodulus of 3,710,000 p.s.i.

EXAMPLE 22

Following generally the procedure of Example 13, a polymerization vesselwith an argon atmosphere was charged with 60 parts of phenylacetylene,54 parts of meta-diethynylbenzene, 6 parts of para-diethynylbenzene, 422parts of benzene and 0.3 part of monochlorobenzene. The solution wasbrought to reflux, then 0.8 part of triphenylphosphine and 0.4 part ofnickel acetylacetonate in benzene were added to the refluxing solution.The reaction was monitored by gas-liquid chromatographic analysis. Threehours after addition of the catalyst, 88.3% of the diethynylbenzene and49.5% of the phenylacetylene had been utilized, and the reaction mixturewas worked up as in Example 13 to obtain 53 parts (46% yield) of lightyellow copolymer. Calculation based on monomer usage showed thecopolymer to contain 64 mol percent of diethynylbenzene and 36 molpercent of phenylacetylene.

A molding composition was prepared from the above prepolymer using 20%of diphenylbutadiyne as acetylenic fluidizer. The composition was moldedand cured following generally the procedure of Example 5. The resultingproduct had an average flexural strength of 17,425 p.s.i. and an averageflexural modulus of 1,920,000 p.s.i.

EXAMPLE 23

Following the procedure of Example 22, a copolymer was prepared from areaction mixture containing 75 parts of diphenylbutadiyne, 22.5 parts ofmeta-diethynylbenzene, 2.5 parts of paradiethynylbenzene, 413 parts ofdioxane, 0.3 part of monochlorobenzene, 0.7 part of triphenylphosphineand 0.3 part of nickel acetylacetonate. Diethynylbenzene usage was 100%and diphenylbutadiyne usage was 83.7%. The light yellow copolymerproduct was obtained in 47% yield and contained 27.8 mol percentdiethynylbenzene and 72.2 mol percent diphenylbutadiyne. Following theprocedure of Example 22, a molding composition was prepared, molded andcured. The cured product had an average flexural strength of 7575 p.s.i.and an average flexural modulus of 460,000 p.s.i.

EXAMPLE 24

The procedure of Example 23 was essentially duplicated except to use32.2 parts of diphenylbutadiyne, 61 parts of meta-diethynylbenzene and6.8 parts of para-diethynylbenzene as the monomer mixture. The catalystcomponents were also reduced to 0.35 part of triphenylphosphine and 0.15part of nickel acetylacetonate, and the reaction time was one hour fromcatalyst addition. The copolymer product contained 68.9 mol percentdiethynylbenzene and 31.1 mol percent diphenylbutadiyne. Following theprocedure of Example 22, a molding composition was prepared from thecopolymer, and the composition was molded and cured. The cured producthad an average flexural strength of 7295 p.s.i. and an average flexuralmodulus of 543,000 p.s.i.

What I claim and desire to protect by Letters Patent is:
 1. Apolyacetylenically unsaturated prepolymer consisting essentially of apolycyclotrimerization polymer of at least one polyacetylenicallysubstituted aromatic compound selected from the group consisting ofdiethynylbenzene; diethynyltoluene; diethynylxylene; diethynylbiphenyl;9,10-diethynylanthracene; 9,10-diethynylphenanthrene;di(ethynylphenyl)ether; 1-chloro-2,5-diethynylbenzene;2,3,5,6-tetrachloro-1,4-diethynylbenzene;4,4'-diethynyl-trans-azobenzene; diphenylbutadiyne;2,2'-dichlorodiphenyldiacetylene; 4,4'-dichlorodiphenyldiacetylene;4,4'-dibromodiphenyldiacetylene; di-p-tolyldiacetylene;di-α-naphthyldiacetylene; dibenzyldiacetylene;1,4-bis(phenylethynyl)benzene; 1,3-bis(phenylethynyl)benzene;9,10-bis(phenylethynyl)anthracene; 1,3,5-triethynylbenzene;1,2,4-triethynylbenzene;1,3,5-tris(phenylethynyl)-2,4,6-triphenylbenzene;1,2,4-tris(phenylethynyl)-3,5,6-triphenylbenzene;tris(ethynylphenyl)benzene and mixtures of at least one of saidcompounds with phenylacetylene, said prepolymer having a number averagemolecular weight of from about 900 to about 12,000, a ratio of aromaticprotons to olefinic protons from about 2.4:1 to about 38:1 andcontaining from about 5 to about 20% terminal acetylenic groups byweight of the prepolymer.
 2. The prepolymer of claim 1 wherein thepolymer of the polyacetylenically substituted aromatic compound is apolymer of a diethynylbenzene.
 3. The prepolymer of claim 2 wherein thepolymer of a diethynylbenzene is a copolymer of a diethynylbenzene anddiphenylbutadiyne.
 4. The prepolymer of claim 2 wherein the polymer of adiethynylbenzene is a copolymer of a diethynylbenzene andphenylacetylene.
 5. A method of producing polyphenyl polymers comprisingpolycyclotrimerization of compounds selected from the group: (1)diethynyl derivatives of aromatic compounds having the formula ##STR1##(2) mixtures of said diethynyl derivatives with the monoethynyl compoundhaving the formula ##STR2## and (3) mixtures of p-diethynylbenzene withm-diethynylbenzene, in the presence of catalysts which are complexcompounds of nickel.
 6. The polyphenyl polymers produced by the methodof claim
 5. 7. A method according to claim 5, wherein the process ofpolycyclotrimerization is carried out in the presence of said catalysttaken in an amount of 1 mole per 25-1250 moles of the starting ethynylcompounds.
 8. A method according to claim 5, wherein the process ofpolycyclotrimerization is carried out in an aromatic compound assolvent.
 9. A method according to claim 8, wherein benzene, toluene ordioxane is used as an aromatic compound.
 10. A method according to claim5, wherein the process is carried out at a temperature ranging from 55°to 250° C.